Available online www.jocpr.com
Journal of Chemical and Pharmaceutical Research, 2013, 5(11):489-496
Research Article
ISSN : 0975-7384
CODEN(USA) : JCPRC5
Voltammetric determination of potassium hydrogenperoxomonosulfate in
pure substance and disinfectant "Ecocide S"
Mykola Ye. Blazheyevskiy and Olena O. Mozgova
Department of Physical and Colloid Chemistry, National University of Pharmacy, Pushkinska str., Kharkiv, Ukraine
_____________________________________________________________________________________________
ABSTRACT
The behavior of potassium hydrogenperoxomonosulfate (KHSO5) has been studied using alternating current
voltammetry with square wave modulation in potential range +1.0…–1.2 V at carbositall electrode as indicating
and auxiliary electrode (reference electrode Ag, AgCl/KСl(sat)) (Ep = +0.25 V). A linear relationship between peak
current and concentration was obtained in the range 0.9×10–5 mol L–1 to 5.4×10–5 mol L–1 of the KHSO5
concentrations at pH ~ 0.8 for pure substance. It is Ip = (8.3 ± 0.6)×103×с (r = 0.999). RSD were 2.68 %, 2.55 % and
2.39 % for the 3.6×10–5, 4.5×10–5 and 5.4×10–5 mol L–1concentrations of KHSO5 model solutions, respectively (δ =
–0.28…+0.44 %). The addition method was used for KHSO5 determination in disinfectant "Ecocid S", RSD were
2.01 % and 1.88 % for с(KHSO5) = 4.65×10–5 and 7.75×10–5 mol L–1, respectively. The obtained results have good
agreement with those obtained by using the reference method of iodometric titration, with an accuracy lower than –
0.42 %.
Keywords: potassium hydrogenperoxomonosulfate, voltammetry, carbositall electrode, disinfectant
_____________________________________________________________________________________________
INTRODUCTION
Potassium hydrogenperoxomonosulfate (KHSO5) is one of the most widely used disinfectants in a medical practice,
among well-known class of chemical disinfectants – oxidants. It is included in the new generation of modern
disinfection agents in the form of a stable triple potassium salt 2KHSO5·KHSO4·K2SO4, such as "Virkon" and its
modified analogue "Ecocid S". Potassium hydrogenperoxomonosulfate is also used as analytical reagent for quantitave
analysis of different pharmaceutical substances such as penicillins, phenothiazines, cephalosporins and etc. [1].
Ecocid S (KRKA, Slovenia, Novo mesto) is a well known universal combination highly active broad-spectrum
disinfectant of the new generation of the oxidant class, which has virulicidal, bactericidal, fungicidal and sporocidal
activity, comprising KHSO5 (50 %) in the form of a triple potassium salt – 2KHSO5·KHSO4·K2SO4 (500 mg to 1 g
of drug) (mass fraction of active oxygen in terms of active chlorine 9.5-15.0 %) as active ingredient and excipients:
surfactant – sodium dodecylbenzenesulfonate, organic acids (malic and sulfamic acids), inorganic buffer systems
(sodium polyphosphate, sodium chloride), an indicator of activity – azo dye and flavor of citron scent. KHSO5 is an
effective biocide; it works against all 18 known families of pathogenic for humans and animals viruses, Grampositive and Gram-negative bacteria, some yeasts and fungi [2-9]. Organic acids in combination with inorganic
buffer creates an acidic environment and optimize the biocidal activity of KHSO5. Sodium dodecylbenzenesulfonate
acts as a surfactant, thus ensuring oxidizer contact with pathogens.
The drug is intended for disinfection of all surfaces that require safe and effective disinfection. It is used for
disinfection of livestock and poultry premises vivariums, pet cages, aquariums, plants for the processing of poultry
and eggs, slaughter and meat processing plants, grain storage, feed mills, vehicles, containers, equipment, surfaces,
appliances, instruments, systems supply drinking water, milk, air sanitation, drinking water and other facilities are
subject to veterinary supervision.
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Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
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It is used as aqueous solutions in the working concentrations of 0.1 to 4 %. To disinfect the hands 0.5 % solution is
recommended.
Determination (mass fraction) of active oxygen (in terms of active chlorine) in the preparation is carried out by
iodometric titration [10].
KHSO5 in the preparation "Virkon" is determined by the technique of pH-potentiometric titration with standard
solution of tin (II) chloride in the presence of potassium bromide using a point platinum and glass electrode [11].
Extensive literature survey reveals that various electrochemical methods have been reported for the determination of
electrochemically active compounds of various classes, including hydrogen peroxide and inorganic peroxides
analysis [12-16]. Among them the method of voltammetry with linear potential scan using a drop mercury electrode
or its other modifications and solid platinum or gold electrodes is most commonly used. These electrodes are
characterized by satisfactory reproducibility of research results and simple methods for their preparation. However,
mercury is a toxic substance and other metals rather expensive. Also is known, that the oxygen chemosorbs on Au,
as well as on Pt, and forms oxide film. Adsorbed oxygen is involved in the anodic process, and Au oxides inhibit
processes of analyte electrooxidation. As a consequence the electrodes based on cheap carbon materials such as
carbon glass, carbon paste, carbositall are widely used [17-20]. They are characterized by high overpotential (low
adsorption capacity in relation to O2 and H2 in the work potential area) of hydrogen and/or oxygen (the ability to
track multiple regeneration to obtain reproducible surface). In addition, these electrodes offer the ability to perform
such analytical definitions which mercury or other electrodes are not always possible to. It has been very popular
because of its excellent electrical and mechanical properties, wide potential range, extreme chemical inertness and
relatively reproducible performance [21-27].
The aim of the present work is to determine the feasibility of quantitative determination of potassium
hydrogenperoxomonosulfate in pure substance and disinfectant "Ecocid S" by cathodic voltammetry using
carbositall electrode (Russia) as indicating (working) electrode.
EXPERIMENTAL SECTION
Instrumentation
Electrochemical measurements were carried out in the analyzer АVS-1.1 (Volta, St. Petersburg) with a threeelectrode scheme by alternating current mode with square wave modulation in potential range +1.0…–1.2 V, W =
1000 rpm, amplitude 40 mV, ν = 65 Hz. The values of potential peaks directly at a maximum are measured by
electrochemical sensor "Module EM-04" with an accuracy of ±5 mV. Carbositall electrode was used as a working
and an auxiliary electrode, and Ag,AgCl/KСl(sat) electrode type EVL-1М4 as a reference electrode.
Scheme of the reduction process is:
HSO 5− + 2 e + 2 H + → HSO 4− + H 2 O
Reagents and Chemicals
All the materials were of analytical reagent grade, and the solutions were prepared with double-distilled water.
Background solution
Background solution is prepared by dissolving 68.1 g of potassium hydrogensulfate (KHSO4) in 500 mL volumetric
flask by double-distilled water to give a concentration of 1 mol L–1.
Stock solution of pure substance
The solution of potassium hydrogenperoxomonosulfate («Oxone®», ACROS ORGANICS) was freshly prepared and
standardized iodometrically. Stock solution were prepared by dissolving 0.1537 g of powder (triple potassium salt,
2KHSO5·KHSO4·K2SO4) in 50 mL volumetric flask by double-distilled water to give a concentration of 9×10–3
mol L–1. 10 mL of 9×10–3 mol L–1 KHSO5 was diluted in 100 mL volumetric flask with double-distilled water to
obtain a solution of 9×10–4 mol L–1 KHSO5.
Working solutions of pure substance
Working standards were prepared by diluting different volumes of stock solution 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 mL
with 10 mL of 1 mol L–1 background solution in 50 mL volumetric flask by double-distilled water.
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Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
______________________________________________________________________________
Stock solution of the sample preparation
The sample preparation which was subjected to the analytical procedures for the analysis of KHSO5 was disinfectant
"Ecocid S" (KRKA, Slovenia, Novo mesto). This solution was prepared by dissolving 0.5 g of preparation (accurate
weight) in 100 mL volumetric flask by double-distilled water to give a concentration of preparation 5 %
(concentration of KHSO5 in mass was 7.75×10–3 mol L–1). 10 mL of this solution was diluted in 100 mL volumetric
flask with double-distilled water to obtain a solution of 7.75×10–4 mol L–1 KHSO5.
Working solutions of the sample preparation
Working solutions were prepared by diluting 3.0 and 5.0 mL of stock solution of the sample preparation with 10 mL
of 1 mol L–1 background solution in 50 mL volumetric flask by double-distilled water.
Analytical procedure
Procedure of pure substance
25 mL of working solution of pure substance was transferred to the cell. The voltammograms were recorded by
scanning the potential toward the negative direction in the potential range from +1.0 V to –1.2V. All data were
obtained at room temperature. The number of experiments (n = 5) according to this value, the statistical calculations
were done for 3.6×10–5, 4.5×10–5 and 5.4×10–5 mol L–1 solutions of KHSO5.
Procedure for sample preparation
A typical procedure involves preparing several solutions containing the same amount of unknown, but different
amounts of standard. For example, five 50 mL volumetric flasks are each filled with 3 mL or 5 mL of the unknown
and then the standard is added in differing amounts, such as 0, 1, 2, and 3 mL. The flasks are then diluted to the
mark and mixed well. 25 mL of each prepared solutions were transferred to the cell. The voltammograms were
recorded by scanning the potential toward the negative direction in the potential range from +1.0 V to –1.2 V. All
data were obtained at room temperature.
RESULTS AND DISCUSSION
Effect of nature and pH of background solution
The effect of pH on the reduction process was investigated by recording voltammograms of KHSO5 at a 5.4×10–5
mol L–1 concentration at several pH values ranging from 0.80 to 7.17 (Fig. 1). A mixture of 0.5 mol L–1 Na2SO4 +
0.05 mol L–1 KHSO4 was used as background solution and the pH of the solution from 0.80 to 7.17 was changed
gradually adding NaOH 0.2 mol L–1. The pH was measured using ionmeter type І-160М (Belarus) with a glass
electrode type ESL-43-07 paired with Ag, AgCl/KСl (sat) electrode.
As can be seen, height of KHSO5 reduction peak at the carbositall electrode surface decreases and potential of
reduction peak is shifted toward more electronegative values with increasing of background electrolyte pH from
0.80 to 7.17.
I, µА
7
10.0
7.5
1
5.0
2.5
0.6
0
0.3
–0.3
Е, V
×10 mol L at different pH values of the background solution: 1 –
Fig. 1. Voltammogram of KHSO5 reduction at a concentration of 5.4×
0.80, 2 – 1.77, 3 – 2.87, 4 – 3.87, 5 – 5.42, 6 – 6.35, 7 – 7.1
–5
491
–1
Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
______________________________________________________________________________
The maximum peak (Ip) occurs at approximately pH 0.8 and at a pH around 5 analytical signal almost disappears
(Fig. 2). The effect of pH on peak potential (Ep) shows the following: when pH value increases in the interval from
0.8 to 2, Ep remains almost constant, but Ep decreases sharply to negative value with pH increasing (Fig. 3). That is
why the optimum pH for analysis is ≤ 2.
I p,µА 0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
2
4
6
8
рН
Fig. 2. Influence of pH on the peak intensity of the reduction process of KHSO5 at the carbositall electrode (reference electrode
Ag,AgCl/KСl(sat))
Е p ,V 0.3
0.2
0.1
0
0
2
4
6
рН
8
-0.1
-0.2
Fig. 3. Influence of pH on the peak potential of the reduction process of KHSO5 at the carbositall electrode (reference electrode
Ag,AgCl/KСl(sat))
Effect of surfactant
Surfactants are a kind of amphiphilic molecule with a polar group on one side and a long hydrophobic tail on the
other. The variety of currently available surfactants and hence their properties makes it possible to use this group of
compounds for controlling analytical signals in voltammetry and, consequently, to increase the sensitivity and
selectivity of the analyte response. The applications of surfactants in electrochemistry and electroanalytical
chemistry have been widely reported [28,29].
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Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
______________________________________________________________________________
6
I, µА
6.0
5.0
4.0
1
2.0
0.4
0.6
0.2
0
Е, V
Fig. 4. Voltammogram of KHSO5 reduction depending on the concentration in the absence (curves 1-3) and in the presence of surfactants
(0.05 % solution of SDBS) (curves 4-6). c(KHSO5), 10–5, mol L–1: 1, 4 – 1.8, 2, 5 – 5.4, 3, 6 – 9.2, with SDBS: 4 – 1.8, 5 – 5.4, 6 – 9.2
(background – 0.2 mol L–1 KHSO4) at carbositall electrode(reference electrode Ag,AgCl/KСl(sat))
The electrochemical responses of KHSO5 at carbositall electrode were shown in Fig. 4 (curves 1-3) with 0.2 M
KHSO4 as background solution. The voltammetric response is apparently improved in the presence of 0.05% sodium
dodecylbenzenesulfonate (SDBS), reflected by the enlargement of current peak (Fig. 4, curves 4-6) and the
reduction peak shifted to more electropositive side from +0.25 V to +0.3 V. The peak current enhancement was
undoubtedly attributed to the interaction of SDBS with KHSO5 and carbositall electrode. It is well known that
surfactants can be adsorbed on hydrophobic surface to form surfactant film, which may alter the overvoltage of the
electrode and influence the rate of electron transfer [30,31]. The probable mechanism is following: the SDBS
surfactant molecule diffuses into the carbositall electrode along with the KHSO5 signal.
Method of quantitative determination of KHSO5 in pure substance
Voltammetric behavior of KHSO5 at carbositall electrode was shown in Fig. 5. The study was conducted in solutions
with a concentration of KHSO5 from 0.9×10–5 to 5.4×10–5 mol L–1. Background solution was KHSO4 (c = 0.2 mol L–
1
, pH ~0.8).
I, µА
6
4.0
3.5
1
3.0
2.5
0.6
0.4
0.2
0
Е, V
Fig. 5. Voltammogram of KHSO5 reduction at carbositall electrode according to the concentration. c (KHSO5), 10–5, mol L–1 1 – 0.9, 2 –
1.8, 3 – 2.7, 4 – 3.6, 5 – 4.5, 6 – 5.4; pH ~0.8 (background is KHSO4, c = 0.2 mol L–1); Ep = 0.25 V (reference electrode Ag, AgCl/KСl(sat))
493
Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
______________________________________________________________________________
The calibration curves method is used to quantify the concentration of KHSO5. The graph was plotted in the
coordinates: the height of peaks Ip in µA at 0.25 V on the ordinate axis and corresponding concentration of KHSO5 c
in mol L–1 on the abscissa axis (Fig. 6).
Regression characteristics of KHSO5 voltammetric determination procedure in pure substance was shown in Tab. 1.
Fig. 6. The calibration plot of the KHSO5 reduction current peak vs. concentration with 0.2 mol L–1 KHSO4 background solution (pH ~
0.8) at carbositall electrode (reference electrode Ag,AgCl/KСl(sat)); Ep = 0.25 V
Table 1: Regression characteristics of KHSO5 voltammetric determination procedure in pure substance
Parameters
Concentration ranges (mol L–1)
Regression equation
Slope (a)
Intercept (b)
∆a
∆b
Sa
Sb
Correlation coefficient (r)
LOD (mol L–1)
LOQ (mol L–1)
Data
(0.9-5.4)×10–5
Ip = (8.3 ± 0.6)×103×с
8.3×103
0.006
0.6×103
0.02
0.2×103
0,007
0.999
2.76×10–6
9.19×10–6
The reproducibility was evaluated from 5 repeated electrochemical signal measurements of model solutions with
3.6×10–5, 4.5×10–5 and 5.4×10–5 mol L–1 concentrations of KHSO5. The precision of the developed method in terms
of the relative standard deviation (RSD) were 2.68 %, 2.55 % and 2.39 % (δ = –0.28…+0.44 %), respectively. The
obtained results are summarized in Tab. 2.
Table 2: Evaluation of accuracy and precision of KHSO5 voltammetric determination procedure in model solution of pure substance
(n = 5; P = 0.95%)
Taken (mol L–1)
3.6×10–5
4.5×10–5
5.4×10–5
Found (mol L–1)
(3.59±0.12)× 10–5
(4.52±0.14)× 10–5
(5.41±0.16)× 10–5
Recovery (%±SD)
99.7±3.3
100.4±3.2
100.2±3.0
494
RSD, %
2.68
2.55
2.39
ε (%)
3.3
3.2
3.0
δ (%)
–0.28
+0.44
+0.19
Mykola Ye. Blazheyevskiy and Olena O. Mozgova
J. Chem. Pharm. Res., 2013, 5(11):489-496
______________________________________________________________________________
Method of quantitative determination of KHSO5 in "Ecocid S"
It was found that SDBS, which is the part of the test solution of sample preparation, cause the KHSO5 reduction
current peak increase, so it was decided to use the addition method for analysis of the preparation.
At first voltammogram of test solution was recorded and then a solution of known aliquots of standard solution Сst
was added and again voltammogram was recorded. The concentration of the test solution Cx is given by the
equation:
Сx = Cst
Ix
,
I x + st − I x
where Ix – current peak of test solution; Ix+st – current peak of test solution with the addition of a standard substance.
The high sensitivity of this method is accompanied by very good reproducibility. During the determination of
4.65×10–5 and 7.75×10–5 mol L-1 KHSO5 in test solutions RSD were 2.01 % and 1.88 % (δ = –0.42…–0.30%),
respectively (n = 5, P = 0.95). The obtained results are summarized in Tab. 3.
Table 3: The results of voltammetric determination of potassium hydrogenperoxomonosulfate in Ecocid S (n = 5; P = 0.95%)
Taken
mol L–1
%*
4.65×10–5 11.01
7.75×10–5 11.01
Found
Recovery (%±SD) RSD, % ε (%)
mol L–1
%*
–5
10.96
99.57±2.49
2.01
2.5
(4.63±0.12)× 10
99.64±2.32
1.88
2.3
(7.72±0.18)× 10–5 10.95
* in terms of active chlorine in preparation [10]
** relative to the average reference method of iodometric titration [10]
δ** (%)
–0.42
–0.30
CONCLUSION
So, new voltammetric method of aqueous solutions of potassium hydrogenperoxomonosulfate determination in pure
substance and disinfectant "Ecocid S" using carbositall electrode as indicating electrode was developed and the
possibility of its quantitative determination was shown.
Linear concentration ranges for pure substance varies from (0.9-5.4)×10–5 mol L–1. Calibration graph is
Ip = (8.3 ± 0.6)×103×с (r = 0.999). RSD were 2.68 %, 2.55 % and 2.39 % for the 3.6×10–5, 4.5×10–5 and 5.4×10–5
mol L–1concentrations of KHSO5 model solutions, respectively (δ = –0.28…+0.44 %). The addition method was used
for KHSO5 determination in disinfectant "Ecocid S", RSD were 2.01 % and 1.88 % for с(KHSO5) = 4.65×10–5 and
7.75×10–5 mol L–1, respectively. The obtained results have good agreement with those obtained by using the reference
method of iodometric titration, with an accuracy lower than –0.42 %.
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